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Federal Register / Vol. 55, No. 126 / Friday, June 29, 1990 / Rules and Regulations

ENVIRONMENTAL PROTECTIONAGENCY

40 CFR Parts 261,264, 265, 268, 271

and 302

[SWH-FRL-3792-2; EPA/OSW-FR-90-014]

RIN 2050-AA78

Hazardous Waste ManagementSystem; Identification and Listing ofHazardous Waste; ToxicityCharacteristic Revisions

AGENCY: Environmental ProtectionAgency.ACTION: Final rule; corrections.

SUMMARY: On March 29, 1990 (55 FR11798), the EnVironmentl ProtectionAgency (EPA) promulgated a rule torevise the existing toxicitycharacteristics, which are used toidentify those wastes which arehazardous and thus subject to regulationunder subtitle C of the ResourceConservation and Recovery Act (RCRA)due to their potential to leach significantconcentrations of specific toxicconstituents. Since promulgation, theAgency has found the need to makecorrections to the rule in order to ensureconsistency of the toxicity characteristicleaching procedure (TCLP), Method1311, with other methods contained inTest Methods for Evaluating SolidWaste (Physical/Chemical Methods),SW-846 and to clarify the section onquality assurance. This notice alsocorrects several errors in the March 29,1990 notice.DATES: Effective date: September 25,1990. The effective date and compliancedates are not changed by this document.FOR FURTHER INFORMATION CONTACT.For general information about thisnotice, contact the RCRA/SuperfundHotline at (800)424-9346 (toll free) or(202) 382-3000 in the Washington, DCmetropolitan area. For information onspecific aspects of this notice, contactSteve Cochran, Office of Solid Waste(OS-332), U.S. Environmental ProtectionAgency, 401 M Street SW, Washington,DC 20460, (202) 475-8551.I. SUPPLEMENTARY INFORMATION:

A. Background

On March 29, 1990 (55 FR 11798), EPApromulgated a rule to revise the existingtoxicity characteristics, which are usedto identify those wastes which arehazardous and thus subject to regulationunder subtitle C of RCRA. The rulebroadened and refined the scope of thehazardous waste regulatory programand fulfilled specific statutory mandatesunder the Hazardous and Solid WasteAmendments of 1984.

Today's notice makes corrections toappendix II of the regulatory language ofthe March 29, 1990 final rule, Method1311, the TCLP. Themethod has beenreorganized to correspond to the currentversion of Test Methods for EvaluatingSolid Waste (Chemical/PhysicalMethods), SW-846. In addition, thequality assurance section has beenrenumbered and has been clarified toeliminate confusion. Today's notice alsocorrects several typographical errorsand other omissions that appeared inthe final rule revising the toxicitycharacteristics.

The preamble to the March 29, 1990final rule stated that any person thatwould like to use the TCLP before theeffective date of the rule (September 25,1990] may do so in order to determinewhether the eight heavy metals and sixpesticides that are currently regulatedunder the Extraction Procedure (EP)Toxicity Characteristic leach at levels ofregulatory concern. This language wasincluded because the TCLP is requiredfor both waste determination (onSeptember 25, 1990, the TC effectivedate) and the land disposal restrictionsprogram. The Agency today is clarifyingthat, while it is appropriate to use justone leach test to fulfill bothrequirements, persons that would like tocontinue using the EP leach test until theeffective date of the TC rule may do so.It should be noted, however, that the EPtest may still be required as a matter ofstate law, and this regulation does notaffect such state law requirements.B. Method 1311 and Quality Assurance

Today's notice makes technicalcorrections to mistakes made in Method1311, and to errors made duringtypesetting, and provides clarificationsto specific procedures of the method.The method also is being reorganized byplacing the leaching procedure in onesection and the quality assurance in aseparate section to conform with theformat used in SW--846.

A correction is being made in thecalculation for the weight of waste tocharge the Zero-Headspace Extractor(ZHE). In the final rule published March29, 1990, the method incorrectly statedthat the optimum sample size to chargeinto the ZHE should be determined forwastes containing >0.5% solids. Thiscalculation results in a charge samplegreater than the capacity of the ZHE.The Agency today is correcting theprocedure to require a determination onwastes containing >5% solids. Thesample holding times and errors madeduring typesetting are also beingcorrected by today's notice.

The Agency received inquiriesindicating that confusion exists

concerning correction factors and howthey should be applied. Therefore, theAgency is making a technical correctionin § 8.2.5 of Method 1311, published intoday's notice, by adding a formula forcorrecting measured values foranalytical bias. Also, inquiries indicatethat EPA's discussion of the appropriateCC and GC/MS methods to be used wasimproper. The preamble language iscorrected by today's notice to indicatethe appropriate CC and GC/MS.methods to be used.

Method 1311 is also being reorganizedby today's notice by placing the leachingprocedure itself in one section, 7.0. (Thesteps of the leaching procedure werepreviously presented in sections 7, 8,and 9 in the March 29, 1990 final rule.) Inaddition, this notice makes minorcorrections to the quality assurancesection and it is renumbered 8.0. Thisreorganization provides consistencywith SW-846.

Appendix II, Method 1311 of theMarch 29, 1990 final rule is replaced inits entirety by Method 1311 of this noticein order to incorporate the corrections,reorganizations, and clarificationswhich are being made by today's notice.

The March 29, 1990 final rule providedan exclusion under 40 CFR 261.4 forpetroleum-contaminated media anddebris that fail the ToxicityCharacteristic. This exclusion appliesonly to petroleum-contaminated mediaand debris which exhibit the TC for anyone or more of the newly identifiedorganic constituents, and which aresubject to corrective action under part280. The regulatory language of thisexclusion in the final rule is revised bytoday's notice to correctly reflect thisapplication.

C. Corrections

1. On page 11798, column one, under"'DATES." in the second line of thecompliance dates paragraph, change"generators: September 25, 1990. Small"to "generators and treatment, storage,and disposal facilities (TSDFs):September 25, 1990. Small".

2. On page 11804, Table II.2-ToxicityCharacteristics Constitutents andRegulatory Levels, change the columnheading "Constituent (mg/L}" to"Constituent".

3. On page 11804, Table II.2-ToxicityCharacteristic Constituents andRegulatory Levels, line twenty, change"Heptachlor (and its hydroxide)" to"Heptachlor (and its epoxide)".

4. On page 11815, column three, TableC-i--Chronic Toxicity ReferenceLevels, lines nineteen and twenty,change "Heptachlor (and its hydroxide)"to "Heptachlor (and its epoxide)".

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Federal Register / Vol. 55, No. 126 / Friday, June 29, 1990 / Rules and Regulations6

5. On page 11825, column one, fourthbullet, first line, change "The dataextracted from RFSs" to "The dataextracted from RFAs".

6. On page 11829, columnn one, thefirst full paragraph (lines twenty-four)through thirty-six) is replaced by thefollowing: "The Agency agrees that theGC method (Method 8040) or the GC/MSmethod (Method 8270) for phenols andthe GC/Electron Capture Detection(GC/ECD) for phenoxyacid herbicides(Method 8150) are more advantageousfor the analysis of these analytesbecause the equipment is more readilyavailable than the HPLC, despite theassociated difficulties. HPLC methodsfor phenols and phenoxyacid herbicidesare not included in the third edition ofSW-846 because of a lack of validationdata. The Agency will allow only theuse of the previously mentioned GC andGC/MS methods (Methods 8040 or 8270)or their equivalents for phenols andMethod 8150 for phenoxyacid herbicidesuntil such time that the Agency proposesan HPLC method."

7. On page 11831, column two,paragraph b, seventh line, change "ruleof 40 CFR 262.3(a)(2)(iv) or the" to "ruleof 40 CFR 261.3(a)(2)(iv) or the".

8. On page 11835, column one, firstand second line, change "July 25, 1985"to "July 15, 1985".

9. On page 11837, column one, thirdcomplete paragraph, thirteenth line,change "for TSDFs on February 5, 1987(53 FR" to "for TSDFs on February 5,1987 (52 FR".

10. On page 11840, column three, firstbullet of second complete paragraph,first line, change "Solid waste that is ahazardous waste" to "Used oil that is ahazardous waste".

11. On page 11844, Table IV-1.--TCConstituent and Regulatory LevelsProposed June 13, 1986-Continued,fourth line, change the CASNO for D034from "76-44-2" to "76-44-8".

12. On page 11844, Table IV-1.-TCConstituent and Regulatory LevelsProposed June 13, 1986--Continued, linetwenty-one, change to read as follows:D045 .... 1,1,1,2-Tetrachloroethane.... 630-20-6 .... 10.0.

13. On page 11844, column two, TableIV-2.-Organic Constituents, fourth line,change the CASNO for D021 from "106-90-7" to "108-90-7".

14. On page 11844, column three,Table IV-2.--Organic Constituents-Continued, first line, change "Do31 ....Heptachlor (and its hydroxide) .... 76-44-2" to "D031 .... Heptachlor (and itsepoxide) .... 76-44-8".

15. On page 11846, Table IV-3-Toxicity Characteristic Constituents andRegulatory Levels-Continued, tenthline, change "Heptachlor (and its

hydroxide)" to "Heptachlor (and itsepoxide)".

16. Also on page 11846, column two,third line, change "270 of chapter 40." to"270 of title 40.".

PART 261-[AMENDED]

§ 261.4 [Correctedl17. On page 11862, column two, in

§ 261.4 paragraph (b)(10), is corrected toread as follows:10. Petroleum-contaminated mediaand debris that fail the test for theToxicity Characteristic of § 261.24(Hazardous Waste Codes D018 throughD043 only) and are subject to thecorrective action regulations under part280 of this chapter.

§ 261.24 [Corrected]18. Also on page 11862, column three,

in § 261.24 Table 1.-MaximumConcentration of Contaminants for theToxicity Characteristic, lines twenty-eight and twenty-nine, change"Heptachlor (and its hydroxide)" to"Heptachlor (and its epoxide)".

PART 271--AMENDED]

§ 271.1 [Corrected]19. On page 11876, in § 271.1(j) Table

1-Regulations Implementing theHazardous and Solid WasteAmendments of 1984, the FederalRegister reference should be "55 FR11798-11877".

PART 302--[AMENDED]

§ 302.4 [Corrected]20. On page 11877, in § 302.4, Table

302.4, List of Hazardous Substances andReportable Quantities, in the firstcolumn, make the following corrections:

A. In the ninth line, change"Heptachlor (and hydroxide) (D031)" to"Heptachlor (and epoxide) (D031)."

B. In line twenty-five, change"Thrichloroethylene (D040)" to"Trichloroethylene (D040)".

C. In line twenty-six, change "2,4,5-Trichlorethylene (D041)" to "2,4,5-Trichlorophenol (D041)".

Dated: June 22,1990.Mary A. Gade,Acting Assistant Administrator.

In addition to the corrections madeabove, part 261 Is amended by revisingappendix H to read as follows:

Appendix i-Method 1311 ToxicityCharacteristic Leaching Procedure(TCLP)

1.0 Scope and Application1.1 The TCLP is designed to determine the

mobility of both organic and inorganic

analytes present in liquid, solid, andmultiphasic wastes.

1.2 If a total analysis of the wastedemonstrates that individual analytes are notpresent in the waste, or that they are presentbut at such low concentrations that theappropriate regulatory levels could notpossibly be exceeded, the TCLP need not berUn.

1.3 If an analysis of any one of the liquidfractions of the TCLP extract indicates that aregulated compound is present at such highconcentrations that, even after accounting fordilution from the other fractions of theextract, the concentration would be equal toor above the regulatory level for thatcompound, then the waste is hazardous and itis not necessary to analyze the remainingfractions-of the extract.

1.4 If an analysis of extract obtainedusing a bottle extractor shows that theconcentration of any regulated volatileanalyte equals or exceeds the regulatorylevel for that compound, then the waste ishazardous and extraction using the ZHE isnot necessary. However, extract from a bottleextractor cannot be used to. demonstrate thatthe concentration of volatile compounds isbelow the regulatory level.

2.0 Summary of Method

2.1 For liquid wastes (i.e., thosecontaining less than 0.5% dry solid material),the waste, after filtration through a 0.6 to 0.8pm glass fiber filter, is defined as the TCLPextract.

2.2 For wastes containing greater than orequal to 0.5% solids, the liquid, if any, isseparated from the solid phase and stored forlater analysis; the particle size of the solidphase is reduced, if necessary. The solidphase is extracted with an amount ofextraction fluid equal to 20 times the weightof the solid phase. The extraction fluidemployed is a function of the alkalinity of thesolid phase of the waste. A special extractorvessel is used when testing for volatileanalytes (see Table I for a list of volatilecompounds). Following extraction, the liquidextract is separated from the solid phase byfiltration through a 0.6 to 0.8 pm glass fiberfilter.

2.3 If compatible (i.e., multiple phases willnot form on combination), the initial liquidphase of the waste is added to the liquidextract, and these are analyzed together. Ifincompatible, the liquids are analyzedseparately and the results are mathematicallycombined to yield a volume-weightedaverage concentration.

3.0 Interferences

3.1 Potential Interferences that may beencountered during analysis are discussed inthe individual analytical methods.

4.0 Apparatus and MAaterials

4.1 Agitation apparatus: The agitationapparatus must be capable of rotating theextraction vessel in an end-over-end fashion(see Figure 1) at 30 12 rpm. Suitable devicesknown to EPA are identified in Table 2.

4.2 Extraction Vessels.4.2.1 Zero-Headspace Extraction Vessel

(ZHE). This device is for use only when thewaste is being tested for the mobility of

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Federal Register / VoL 55, No. 126 I Friday, June 29, 1990 1 Rules and Regulations

volatile analytes (i.e., those listed in Table 1).The ZHE (depicted in Figure 2) allows forliquid/solid separation within the device, andeffectively precludes headspace. This type ofvessel allows for initial liquid/solidseparation, extraction. and final extractfiltration without opening the vessel (seesection 4.31). The vessels shall have aninternal volume of 500-600 mL, and beequipped to accommodate a 90-110 mm filter.The devices contain VITON01 O-rings whichshould be replaced frequently. Suitable ZHEdevices known to EPA are identified in Table3.

For the ZHE to be acceptable for use, thepiston within the ZHE should be able to bemoved with approximately 15 pounds persquare inch (psi) or less. If it takes morepressure to move the piston, the 0-rings inthe device should be replaced. If this does notsolve the problem, the ZHE is unacceptablefor TCLP analyses and the manufacturershould be contacted.

The ZHE should be checked for leaks afterevery extraction, If the device contains abuilt-in pressure gauge, pressurize the deviceto 50 psi, allow it to stand unattended for 1hour, and recheck the pressure. If the devicedoes not have a built-in pressure gauge.pressurize the device to 50 psi, submerge it inwater, and check for the presence of airbubbles escaping from any of the fittings. Ifpressure is lost. check all fittings and inspectand replace O-rings, if necessary. Retest thedevice. If leakage problems cannot be solved,the manufacturer should be contacted.

Some ZHEs use gas pressure to actuate theZHE piston, while others use mechanicalpressure (see Table 3). Whereas the volatilesprocedures (see section 7.3) refers to poundsper square inch (psi), for the mechanicallyactuated piston, the pressure applied ismeasured in torque-inch-pounds Refer to themanufacturer's instructions as to the properconversion.

4Z2 Bottle Extraction Vessel When thewaste is being evaluated using thenonvolatile extraction, a jar with sufficientcapacity to hold the sample and theextraction fluid is needed. Headspace isallowed in this vessel

The extraction bottles may be constructedfrom various materials, depending on theanalyte to be analyzed and the nature of thewaste tsee section 4.3.3). It is recommendedthat borosiicate glass bottles be used insteadof other types of glass, especially wheninorganics are of concern. Plastic bottles,other than polytetrafluoroethylene, shall notbe used if organics are to be investigated.Bottles are available from a number oflaboratory suppliers. When this type ofextraction vessel is used. the filtration devicediscussed n section 4.3.2 is used for initialliquid/solid separation and final extractfiltration.

4.3 Filtration Devices: It is recommendedthat all filtrations be performed in a hood.

4.3.1 Zero-Headspace Extractor Vessel(ZHEJ When the waste is evaluated forvolatiles, the zero-headspace extractionvessel described in section 4±1 is used forfiltration. The device shall be capable ofsupporting and keeping in place the glass

I VITONO Is a registered trademark dF DuPont.

fiber filter and be able to withstand thepressure needed to accomplish separation (50psi).

Note: When it is suspected that the glassfiber filter has been ruptured, an in-line glassfiber filter may be used to filter the materialwithin the ZHE.

4.3.2 Filter Holder: When the waste isevaluated for other than volatile analytes,any filter holder capable of supporting a glassfiber filter and able to withstand the pressureneeded to accomplish separation may beused. Suitable filter holders range fromsimple vacuum units to relatively complexsystems capable of exerting pressures of upto 50 psi or more. The type of filter holderused depends on the properties of thematerial to be filtered [see section 4.3.3).These devices shall have a minimum internalvolume of 300 mL and be equipped toaccommodate a minimum filter size of 47 mm(filter holders having an internal capacity of1.5 L or greater, and equipped toaccommodate a 142 mnm diameter filter, arerecommended). Vacuum filtration can only beused for wastes with low solids content(<10%) and for highly granular, liquid-containing wastes. All other types of wastesshould be filtered using positive pressurefiltration. Suitable filter holders known toEPA are shown in Table 4.

4.3.3 Materials of Construction:Extraction vessels and filtration devices shallbe made of inert materials which will notleach or absorb waste components. Glass,polytetrafluoroethylene (PTFE). or type 316stainless steel equipment may be used whenevaluating the mobility of both organic andinorganic components. Devices made of highdensity polyethylene [HDPE), polypropylene(PP), or polyvinyl chloride (PVC) may be usedonly when evaluating the mobility of metals.Borosilicate glass bottles are recommendedfor use over other types of glass bottles,especially when inorganics are analytes ofconcern.

4.4 Filters: Filters shall be made ofborosilicate glass fiber, shall contain nobinder materials, and shall have an effectivepore size of 0.6 to 0.8 pro. or equivalent.Filters known to EPA which meet thesespecifications are identified in Table 5. Pre-filters must not be used. When evaluating themobility of metals, filters shall be acid-washed prior to use by rinsing with IN nitricacid followed by three consecutive rinseswith deionized distilled water (a minimum of1 L per rinse is recommended). Glass fiberfilter are fragile and should be handled withcare.

4.5 pH Meters: The meter should beaccurate to - 0.05 units at 25°C.

4.6 ZHE Extract Collection Devices:TEDLAR bags or glass, stainless steel orPTFE gag-tight syringes are used to collectthe initial liquid phase and the final extract ofthe waste when using the ZHE device. Thedevices listed are recommended for useunder the following conditions:

4.6.1 If a waste contains an aqueousliquid phase or if a waste does not contain asignificant amount of nonaqueous liquid (i.e.,<1% of total waste, the TEDLAR® bag or a

2 TEDLAR@ is a registered trademark of Dupont

600 ml. syringe should be used to collect andcombine the initial liquid and solid extract

4.6.2 If a waste contains a significantamount of nonaqueous liquid in the initialliquid phase (i.e., >1% of total waste), thesyringe or the TEDLAR® bag may be usedfor both the intitial solid/liquid separationand the final extract filtration. However.analysts should use one or the other, notboth.

4.Z.3 If the waste contains no initial liquidphase (is 100% solid) or has no significantsolid phase (is 100% liquid). either theTEDLAR® bag or the syringe maybe used. ifthe syringe is used, discard the first 5 ml. ofliquid expressed from the device. Theremaining aliquots are used for analysis.

4.7 ZHE Extraction Fluid TransferDevices: Any device capable of transferringthe extraction fluid into the ZHE withoutchanging the nature of the extraction fluid isacceptable (e.g. a positive displacement orperistaltic pump, a gas tight syringe, pressurefiltration unit (see section 4.3.2), or other ZHEdevice).

4.8 Laboratory Balance- Any laboratorybalance accurate to within k 0.01 grams maybe used (all weight measurements are to bewithin - 0.1 grams).

4.9 Beaker or Erlenmeyer flask, glass, 500mL

4.10 Watchglass appropriate diameter tocover beaker or erlenmeyer flask.

4.11 Magnetic stirrer.

5.0 Reagents5.1 Reagent grade chemicals shall be used

in all tests. Unless otherwise indicated, it isintended that all reagents shall conform tothe specifications of the Committee onAnalytical Reagents of the AmericanChemical Society, where such specificationsare available. Other grades may be used,provided it is first ascertained that thereagent is of sufficiently high purity to permitits use without lessening the accuracy of thedetermination.

5.2 Reagent water. Reagent water isdefined as water in which an interferant isnot observed at or above the methodsdetection limit of the analytefs) of interest.For nonvolatile extractions, ASTM Type IIwater or equivalent meets the definition ofreagent water. For volatile extractions, it isrecommended that reagent water begenerated by any of the following methods.Reagent water should be monitoredperiodically for impurities.

5.2.1 Reagent water for volatileextractions may be generated by passing tapwater through a carbon filter bedcontainingabout 500 grams of activated carbon (CalgonCorp. Filtrasorb-300 or equivalent).

5.2.2 A water purification system(Millipore Super-Q or equivalent) may also beused to generate reagent water for volatileextractions.

5.2.3 Reagent water for volatileextractions may also be prepared by boilingwater for 15 minutes. Subsequently, whilemaintaining the water temperature at 90 + 5degrees C, bubble a contaminant-free inertgas (e.g., nitrogen) through the water for Ihour. While still hot, transfer the water to anarrow mouth screw-cap bottle under zero-

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headspace and seal with a Teflon-linedseptum and cap.

5.3 Hydrochloric acid (IN), HC1, madefrom ACS reagent grade.

5.4 Nitric acid (IN), HNO 3, made fromACS reagent grade.

5.5 Sodium hydroxide (IN), NaOH, madefrom ACS reagent grade.

5.6 Clacial acetic acid, C-ICH200H,ACS reagent grade.

5.7 Extraction fluid.5.7.1 Extraction fluid #1: Add 5.7 mL

glacial CH 3CH 2 00H to 500 mL of reagentwater (See section 5.2), add 64.3 mL of INNaOH, and dilute to a volume of I liter.When correctly prepared, the pH of this fluidwill be 4.93±0.05.

5.7.2 Extraction fluid #2: Dilute 5.7 mLglacial CIsCF-OOH with reagent water (Seesection 5.2) to a volume of I liter. Whencorrectly prepared, the pH of this fluid will be2.88±0.05.

Note: These extraction fluids should bemonitored frequently for impurities. The pHshould be checked prior to use to ensure thatthese fluids are made up accurately. Ifimpurities are found or the pH is not withinthe above specifications, the fluid shall bediscarded and fresh extraction fluid prepared.

5.8 Analytical standards shall beprepared according to the appropriateanalytical method.

6.0 Sample Collection, Preservation, andHandling

6.1 All samples shall be collected usingan appropriate sampling plan.

6.2 The TCLP may place requirements onthe minimal size of the field sample,depending upon the physical state or states ofthe waste and the analytes of concern. Analiquot is needed for preliminary evaluationof which extraction fluid is to be used for thenonvolatile analyte extraction procedure.Another aliquot may be needed to actuallyconduct the nonvolatile extraction (seesection 1.4 concerning the use of this extractfor volatile organics). If volatile organics areof concern, another aliquot may be needed.Quality control measures may requireadditional aliquots. Further, it is always wiseto collect more samples just in casesomething goes wrong with the initial attemptto conduct the test.

6.3 Preservatives shall not be added tosamples before extraction.

6.4 Samples may be refrigerated unlessrefrigeration results in irreversible physicalchange to the waste. If precipitation occurs,the entire sample (including precipitate)should be extracted.

6.5 When the waste is to be evaluated forvolatile analytes, care shall be taken tominimize the loss of vo'latiles. Samples shallbe collected and stored in a manner intendedto prevent the loss of volatile analytes (e.g.,

samples should be collected in Teflon-linedseptum capped vials and stored at 4 *C.Samples should be opened only immediatelyprior to extraction).

6.6- TCLP extracts should be prepared foranalysis and analyzed as soon as possiblefollowing extraction. Extracts or portions ofextracts for metallic analyte determinationsmust be acidified with nitric acid to a pH <2,unless precipitation occurs (see section 7.2.14if precipitation occurs). Extracts should bepreserved for other analytes according to theguidance given in the individual analysismethods. Extracts or portions of extracts fororganic analyte determinations shall not beallowed to come into contact with theatmosphere (i.e., no headspace) to preventlosses. See section 8.0 (QA requirements) foracceptable sample and extract holding times.

7.0 Procedure7.1 Preliminary Evaluations. Perform

preliminary TCLP evaluations on a minimum100 gram aliquot of waste. This aliquot maynot actually undergo TCLP extraction. Thesepreliminary evaluations include: (1)Determination of the percent solids (section7.1.1); (2) determination of whether the wastecontains insignificant solids and is, therefore,its own extract after filtration (section 7.1.2);(3) determination of whether the solid portionof the waste requires particle size reduction(section 7.1.3); and (4) determination of whichof the two extraction fluids are to be used forthe nonvolatile TCLP extraction of the waste(section 7.1.4.).

7.1.1 Preliminary determination of percentsolids: Percent solids is defined as thatfraction of a waste sample (as a percentageof the total sample) from which no liquid maybe forced out by an applied pressure, asdescribed below.

7.1.1.1 If the waste will obviously yield noliquid when subjected to pressure filtration(i.e., is 100% solids) proceed to section 7.1.3.

7.1.1.2 If the sample is liquid ormultiphasic, liquid/solid separation to makea preliminary determination of percent solidsis required. This involves the filtration devicedescribed in section 4.3.2 and is outlined insections 7.1.1.3 through 7.1.1.9.

7.1.1.3 Pre-weigh the filter and thecontainer that will receive the filtrate.

7.1.1.4 Assemble the filter holder andfilter following the manufacturer'sinstructions. Place the filter on the supportscreen and secure.

7.1.1.5 Weigh out a subsample of thewaste (100 gram minimum) and record theweight.

7.1.1.6 Allow slurries to stand to permitthe solid phase to settle. Wastes that settleslowly may be centrifuged prior to filtration.Centrifugation is to be used only as an aid tofiltration. If used, the liquid should bedecanted and filtered followed by filtration of

the solid portion of the waste through thesame filtration system.

7.1.1.7 Quantitatively transfer the wastesample to the filter holder (liquid and solidphases). Spread the waste sample evenlyover the surface of the filter. If filtration ofthe waste at 4 °C reduces the amount ofexpressed liquid over what would beexpressed at room temperature then allowthe sample to warm up to room temperaturein the device before filtering.

Note: If waste material (>1% of originalsample weight) has obviously adhered to thecontainer used to transfer the sample to thefiltration apparatus, determine the weight ofthis residue and subtract it from the sampleweight determined in section 7.1.1.5 todetermine he weight of the waste sample thatwill be filtered.

Gradually apply vacuum or gentle pressureof 1-10 psi, until air or pressurizing gas movesthrough the filter. If this point is not reachedunder 10 psi, and if no additional liquid haspassed through the filter in any 2 minuteinterval, slowly increase the pressure in 10psi increments to a maximum of 50 psi. Aftereach incremental increase of 10 psi, if thepressurizing gas has not moved through thefilter, and if no additional liquid has passedthrough the filter in any 2 minute interval,proceed to the next 10 psi increment. Whenthe pressurizing gas begins to move throughthe filter, or when liquid flow has ceased at50 psi (i.e., filtration does not result in anyadditional filtrate within any 2 minuteperiod), stop the filtration.

Note: Instantaneous application of highpressure can degrade the glass fiber filter andmay cause premature plugging.

7.1.1.8 The material in the filter holder isdefined as the solid phase of the waste, andthe filtrate is defined as the liquid phase.

Note: Some wastes, such as oily wastesand some paint wastes, will obviouslycontain some material that appears to be aliquid. Even after applying vacuum orpressure filtration, as outlined in section7.1.1.7, this material may not filter. If this isthe case, the material within the filtrationdevice is defined as a solid. Do not replacethe original filter with a fresh filter under anycircumstances. Use only one filter.

7.1.1.9 Determine the weight of the liquidphase by subtracting the weight of the filtratecontainer (see section 7.1.1.3) from the totalweight of the filtrate-filled container.Determine the weight of the solid phase ofthe waste sample by subtracting the weightof the liquid phase from the weight of thetotal waste sample, as determined in section7.1.1.5 or 7.1.1.7.

Record the weight of the liquid and solidphases. Calculate the percent solids.asfollows:

Percent solids =Weight of solid (section 7.1.1.9)

Total weight of waste (section 7.1.1.5 or 7.1.1.7)X 100

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7.1.2 If the percent solids determined insection 7.1.1.9 is equal to or greater than 0.5%,then proceed either to section 7.1.3 todetermine whether the solid material requiresparticle size reduction or to section 7.1.2.1 if itis noticed that a small amount of the filtrateis entrained in wetting of the filter. If thepercent solids determined in section 7.1.1.9 isless than 0.5%. then proceed to section 7.2.9 if

the nonvolatile TCLP is to be performed andto section 7.3 with a fresh portion of thewaste if the volatile TCLP is to be performed.

7.1.2.1 Remove the solid phase and filterfrom the filtration apparatus.

7.1.2.2 Dry the filter and solid phase at100± 20°C until two successive weighingsyield the same value within ± 1%. Record thefinal weight.

Note: Caution should be taken to ensurethat the subject solid will not flash uponheating. It is recommended that the dryingoven be vented to a hood or otherappropriate device.

7.1.2.3 Calculate the percent dry solids asfollows:

% dry solids =(Weight of dry waste+filter)-tared weight of filter

Initial weight of waste (section 7.1.1.5 or 7.1.1.7)

7.1.2.4 If the percent dry solids is lessthan 0.5%, then proceed to section 7.2.9 if thenonvolatile TCLP is to be performed, and tosection 7.3 if the volatile TCLP is to beperformed. If the percent dry solids is greaterthan or equal to 0.5%, and if the nonvolatileTCLP is to be performed, return to thebeginning of this section (7.1) and, with afresh portion of waste, determine whetherparticle size reduction is necessary (section7.1.3) and determine the appropriateextraction fluid (section 7.1.4). If only thevolatile TCLP is to be performed, see the notein section 7.1.4.

7.1.3 Determination of whether the wasterequires particle size reduction (particle sizeis reduced during this step): Using the solidportion of the waste, evaluate the solid forparticle size. Particle size reduction isrequired, unless the solid has a surface areaper gram of material equal to or greater than3.1 cm 2 , or is smaller than I cm in itsnarrowest dimension (i.e., is capable ofpassing through a 9.5 mm (0.375 inch)standard sieve). If the surface area is smalleror the particle size larger than describedabove, prepare the solid portion of the wastefor extraction by crushing, cutting, or grindingthe waste to a surface area or particle size asdescribed above. If the solids are preparedfor organic volatiles extraction, specialprecautions must be taken (see section 7.3.6).

Note: Surface area criteria are meant forfilamentous (e.g., paper, cloth, and similar)waste materials. Actual measurement ofsurface area is not required, nor is itrecommended. For materials that do notobviously meet the criteria, sample-specificmethods would need to be developed andemployed to measure the surface area. Suchmethodology is currently not available.

7.1.4 Determination of appropriateextraction fluid: If the solid content of thewaste is greater than or equal to 0.5% and ifthe sample will be extracted for nonvolatileconstituents (section 7.2), determine theappropriate fluid (section 5.7) for thenonvolatiles extraction as follows:

Note: TCLP extraction for volatileconstituents uses only extraction fluid 4f1(section 5.7.1). Therefore, if TCLP extractionfor nonvolatiles is not required, proceed tosection 7.3.

7.1.4.1 Weigh out a small subsample ofthe solid phase of the waste, reduce the solid(if necessary) to a particle size ofapproximately 1 mm in diameter or less, andtransfer 5.0 grams of the solid phase of the

waste to a 500 mL beaker or Erlerneyerflask.

7.1.4.2 Add 96.5 mL of reagent water tothe beaker, cover with a watchglass, and stirvigorously for 5 minutes using a magneticstirrer. Measure and record the pH. If the pHis <5.0, use extraction fluid #1. Proceed tosection 7.2.

7.1.4.3 If the pH from section 7.1.4.2 is> 5.0. add 3.5 mL iN NCI, slurry briefly, coverwith a watchglass, heat to 50"C, and hold at50°C for 10 minutes.

7.1.4.4 Let the solution cool to roomtemperature and record the pH. If the pH is<5.0, use extraction fluid #1. If the pH is> 5.0, use extraction fluid #2. Proceed tosection 7.2.

7.1.5 If the aliquot of the waste used forthe preliminary evaluation (sections 7.1.1-7.1.4) was determined to be 100% solid atsection 7.1.1.1, then it can be used for thesection 7.2 extraction (assuming at least 100grams remain), and the section 7.3 extraction(assuming at least 25 grams remain). If thealiquot was subjected to the procedure insection 7.1.1.7. then another aliquot shall beused for the volatile extraction procedure insection 7.3. The aliquot of the wastesubjected to the procedure in section 7.1.1.7might be appropriate for use for the section7.2 extraction If an adequate amount of solid(as determined by section 7.1.1.9) wasobtained. The amount of solid necessary isdependent upon whether a sufficient amountof extract will be produced to support theanalyses. If an adequate amount of solidremains, proceed to section 7.2.10 of thenonvolatile TCLP extraction.

7.2 Procedure When Volatiles are notInvolved. A minimum sample size of 100grams (solid and liquid phases) isrecommended. In some cases, a larger samplesize may be appropriate, depending on thesolids content of the waste sample (percentsolids, See section 7.1.1). whether the initialliquid phase of the waste will be misciblewith the aqueous extract of the solid, andwhether inorganics, semivolatile organics,pesticides, and herbicides are all analytes ofconcern. Enough solids should be generatedfor extraction such that the volume of TCLPextract will be sufficient to support all of theanalyses required. If the amount of extractgenerated by a single TCLP extraction willnot be sufficient to perform all of theanalyses, more than one extraction may beperformed and the extracts from eachcombined and aliquoted for analysis.

7.2.1 If the waste will obviously yield noliquid when subjected to pressure filtration(i.e., is 100% solid, see section 7.1.1), weighout a subsample of the waste (100 gramminimum) and proceed to section 7.2.9.

7.2.2 If the sample is liquid or multiphasic,liquid/solid separation is required. Thisinvolves the filtration device described insection 4.3.2 and is outlined in sections 7.2.3to 7.2.8.

7.2.3 Pre-weigh the container that willreceive the filtrate.

7.2.4 Assemble the filter holder and filterfollowing the manufacturer's instructions.Place the filter on the support screen andsecure. Acid-wash the filter if evaluating themobility of metals (see section 4.4).

Note: Acid-washed filters may be used forall nonvolatile extractions even when metalsare not of concern.

7.2.5 Weigh out a subsample of the waste(100 gram minimum) and record the weight. Ifthe waste contains <0.5% dry solids (section7.1.2), the liquid portion of the waste, afterfiltration, is defined as the TCLP extract.Therefore, enough of the sample should befiltered so that the amount of filtered liquidwill support all of the analyses required ofthe TCLP extract. For wastes containing>0.5% dry solids (sections 7.1.1 or 7.1.2), usethe percent solids information obtained insection 7.1.1 to determine the optimumsample size (100 gram minimum) for filtration.Enough solids should be generated byfiltration to support the analyses to beperformed on the TCLP extract.

7.2.6 Allow slurries to stand to permit thesolid phase to settle. Wastes that settleslowly may be centrifuged prior to filtration.Use centrifugation only as an aid to filtration.If the waste is centrifuged, the liquid shouldbe decanted and filtered followed byfiltration of the solid portion of the wastethrough the same filtration system.

7.2.7 Quantitatively transfer the wastesample (liquid and solid phases) to the filterholder (see section 4.3.2). Spread the wastesample evenly over the surface of the filter. Iffiltration of the waste at 4 °C reduces theamount of expressed liquid over what wouldbe expressed at room temperature, thenallow the sample to warm up to roomtemperature in the device before filtering.. Note: If waste material (> 1% of the originalsample weight) has obviously adhered to thecontainer used to transfer the sample to thefiltration apparatus, determine the weight of

^ ,IUU

26990



this residue and subtract it from the sampleweight determined in section 7.2.5, todetermine the weight of the waste samplethat will be filtered.

Gradually apply vacuum or gentle pressureof 1-10 psi, until air or pressurizing gas movesthrough the filter. If this point is reachedunder 10 psi, and if no additional liquid haspassed through the filter in any 2 minuteinterval slowly increase the pressure in 10psi Increments to a maximum of 50 psi. Aftereach incremental increase of 10 psi, if thepressurizing gas has not moved through thefilter, and if no additional liquid has passedthrough the filter in any 2 minute interval,proceed to the next 10 psi increment. Whenthe pressurizing gas begins to move throughthe filter, or when the liquid flow has ceasedat 50 psi (i.e., filtration does not result in anyadditional filtrate within a 2 minute period),stop the filtration.

Note: Instantaneous application of highpressure can degrade the glass fiber filter andmay cause premature plugging.

7.2.8 The material In the filter holder isdefined as the solid phase of the waste, andthe filtrate is defined as the liquid phase.Weigh the filtrate. The liquid phase may nowbe either analyzed (See section 7.2.12) orstored at 4*C until time of analysis.

Note: Some wastes, such as oily wastesand some paint wastes, will obviouslycontain some material that appears to be aliquid. Even after applying vacuum orpressure filtration, as outlined in section 7.2.7,this material may not filter. If this is the case,the material within the filtration device isdefined as a solid and is carried through theextraction as a solid. Do not replace theoriginal filter with a fresh filter under anycircumstances. Use only one filter.

7.2.9 If the waste contains <0.5% drysolids (see section 7.1.2), proceed to section7.2.13. If the waste contains >0.5% dry solids(see section 7.1.1 or 7.1.2), and if particle sizereduction of the solid was needed in section7.1.3, proceed to section 7.2.10. If the waste asreceived passes a 9.5.ram sieve,

quantitatively transfer the solid material intothe extractor bottle along with the filter usedto separate the initial liquid from the solidphase, and proceed to section 7.2.11.

7.2.10 Prepare the solid portion of thewaste for extraction by crushing, cutting, orgrinding the waste to a surface area orparticle size as described in section 7.1.3.When the surface area or particle size hasbeen appropriately altered, quantitativelytransfer the solid material into an extractorbottle. Include the filter used to separate theinitial liquid from the solid phase.

Note: Sieving of the waste is not normallyrequired. Surface area requirements aremeant for filamentous (e.g., paper, cloth) andsimilar waste materials. Actual measurementof surface area is not recommended. Ifsieving is necessary, a Teflon-coated sieveshould be used to avoid contamination of thesample.

7.2.11 Determine the amount of extractionfluid to add to the extractor vessel as follows:

Weight of extraction fluid =20 X percent solids (section 7.1.1) X weight of waste filtered (section 7.2.5 or 7.2.7)

Slowly add this amount of appropriateextraction fluid (see section 7.1.4) to theextractor vesseL Close the extractor bottletightly (it is recommended that Teflon tape beused to ensure a tight seal), secure in rotaryagitation device, and rotate at 30 ± 2 rpm for18 ± 2 hours. Ambient temperature (i.e.,temperature of room in which extractiontakes place) shall be maintained at 23 ± 2°Cduring the extraction period.

Note: As agitation continues, pressure maybuild within the extractor bottle for sometypes of wastes (e.g., limed or calciumcarbonate containing waste may evolvegases such as carbon dioxide). To relieveexcess pressure, the extractor bottle may beperiodically opened (e.g., after 15 minutes. 30minutes, and I hour) and vented into a hood.

7.2.12 Following the 18 ± 2 hourextraction, separate the material in theextractor vessel into its component liquid andsolid phases by filtering through a new glassfiber filter, as outlined in section 7.2.7. Forfinal filtration of the TCLP extract, the glassfiber filter may be changed, if necessary, tofacilitate filtration. Filter(s) shall be acid-washed (see section 4.4) if evaluating themobility of metals.

7.2.13 Prepare the TCLP extract asfollows:

7.2.13.1 If the waste contained no initialliquid phase, the filtered liquid materialobtained from section 7.2.12 is defined as theTCLP extract. Proceed to section 7.2.14.

7.2.13.2 If compatible (e.g., multiplephases will not result on combination),combine the filtered liquid resulting fromsection 7.2.12 with the initial liquid phase ofthe waste obtained in section 7.2.7. Thiscombined liquid is defined as the TCLPextract. Proceed to section 7.2.14.

7.2.13.3 If the initial liquid phase of thewaste, as obtained from section 7.2.7, is not

or may not be compatible with the filteredliquid resulting from section 7.2.12 do notcombine these liquids. Analyze these liquids,collectively defined as the TCLP extract, andcombine the results mathematically, asdescribed in section 7.2.14.

7.2.14 Following collection of the TCLPextract, the pH of the extract should berecorded. Immediately aliquot and preservethe extract for analysis. Metals aliquots mustbe acidified with nitric acid to pH <2. Ifprecipitation is observed upon addition ofnitric acid to a small aliquot of the extract,then the remaining portion of the extract formetals analyses shall not be acidified and theextract shall be analyzed as soon as possible.All other aliquots must be stored underrefrigeration (4 °C) until analyzed. The TCLPextract shall be prepared and analyzedaccording to appropriate analytical methods.TCLP extracts to be analyzed for metals shallbe acid digested except in those instanceswhere digestion causes loss of metallicanalytes. If an analysis of the undigestedextract shows that the concentration of anyregulated metallic analyte exceeds theregulatory level. then the waste is hazardousand digestion of the extract is not necessary.However, data on undigested extracts alonecannot be used to demonstrate that the wasteis not hazardous. If the individual phases areto be analyzed separately, determine thevolume of the individual phases (to ± 0.5%),conduct the appropriate analyses, andcombine the results mathematically by usinga simple volume-weighted average:

Final Analyte (V.)(C1)+(V 2 )(C2)Concentration - V +V 2

where:

Vi =The volume of the first phase (L).C1 =The concentration of the analyte of

concern in the first phase (mg/L).V2 =The volume of the second phase (L).C2=The concentration of the analyte of

concern in the second phase (mg/L).7.2.15 Compare the analyte

concentrations in the TCLP extract with thelevels identified in the appropriateregulations. Refer to section 8.0 for qualityassurance requirements.

7.3 Procedure When Volatiles areInvolved. Use the ZHE device to obtain TCLPextract for analysis of volatile compoundsonly. Extract resulting from the use of the;HE shall not be used to evaluate themobility of nonvolatile analytes (e.g., metals,pesticides, etc.).

The ZHE device has approximately a 500mL internal capacity. The ZHE can thusaccommodate a maximum of 25 grams ofsolid (defined as that fraction of a samplefrom which no additional liquid may beforced out by an applied pressure of 50 psi),due to the need to add an amount ofextraction fluid equal to 20 times the weightof the solid phase.

Charge the ZHE with sample only once anddo not open the device until the final extract(of the solid) has been collected. Repeatedfilling of the ZHE to obtain 25 grams of solidis not permitted.

Do not allow the waste, the initial liquidphase, or the extract to be exposed to theatmosphere for any more time than isabsolutely necessary. Any manipulation ofthese materials should be done when cold(4°C) to minimize loss of volatiles.

7.3.1 Pre-weigh the (evacuated) filtratecollection container (See section 4.6) and setaside. If using a TEDLARI bag, express allliquid from the ZHE device into the bag,

26991



whether for the initial or final liquid/solidseparation, and take an aliquot from theliquid in the bag for analysis. The containerslisted in section 4.6 are recommended for useunder the conditions stated in sections 4.6.1-4.6.3.

7.3.2 Place the ZHE piston within thebody of the ZHE (it may be helpful first tomoisten the piston O-rings slightly withextraction fluid). Adjust the piston within theZHE body to a height that will minimize thedistance the piston will have to move oncethe ZHE is charged with sample (based uponsample size requirements determined fromsection 7.3, section 7.1.1 and/or 7.1.2). Secure

the gas inlet/outlet flange (bottom flange)onto the ZHE body in accordance with themanufacturer's instructions. Secure the glassfiber filter between the support screens andset aside. Set liquid inlet/outlet flange (topflange) aside.

7.3.3 If the waste is 100% solid (seesection 7.1.1), weigh out a subsample (25gram maximum) of the waste, record weight,and proceed to section 7.3.5..

7.3.4 If the waste contains <5% dry solids(section 7.1.2), the liquid portion of waste,after filtration, is defined as the TCLPextract. Filter enough of the sample so thatthe amount of filtered liquid will support all

of the volatile analyses required. For wastescontaining >5% dry solids (sections 7.1.1and/or 7.1.2), use the percent solidsinformation obtained in section 7.1.1 todetermine the optimum sample size to chargeinto the ZHE. The recommended sample sizeis as follows:

7.3.4.1 For wastes containing <5% solids(see Section 7.1.1), weigh out a 500 gramsubsample of waste and record the weight.

7.3.4.2 For wastes containing >5% solids(see Section 7.1.1), determine the amount ofwaste to charge into the ZHE as follows:

25Weight of waste to charge ZHE p X100

percent solids (section 7.1.1)

Weigh out a subsample of the waste of theappropriate size and record the weight.

7.3.5 If particle size reduction of the solidportion of the waste was required in section7.1.3, proceed to section 7.3.6. If particle sizereduction was not required in section 7.1.3,proceed to section 7.3.7.

7.3.6 Prepare the waste for extraction bycrushing, cutting, or grinding the solid portionof the waste to a surface area or particle sizeas described in section 7.1.3.1. Wastes andappropriate reduction equipment should berefrigerated, if possible, to 4C prior toparticle size reduction. The means used toeffect particle size reduction must notgenerate heat in and of itself. If reduction ofthe solid phase of the waste is necedsary,exposure of the waste to the atmosphereshould be avoided to the extent possible.

Note: Sieving of the waste is notrecommended due to the possibility thatvolatiles inay be lost. The use of anappropriately graduated ruler isrecommended as an acceptable alternative.Surface area requirements are meant forfilamentous (e.g., paper, cloth) and similarwaste materials. Actual measurement ofsurface area is not recommended.

When the surface area or particle size hasbeen appropriately altered, proceed tosection 7.3.7.

7.3.7 Waste slurries need not be allowedto stand to permit the solid phase to settle.Do not centrifuge wastes prior to filtration.

7.3.8 Quantitatively transfer the entiresample (liquid and solid phases) quickly tothe ZHE. Secure the filter and supportscreens onto the top flange of the device and

secure the top flange to the ZHE body iiaccordance with the manufacturer'einstructions. Tighten all ZHE fittirgs andplace the device in the vertical position (gasinlet/outlet flange on the bottom). Do notattach the extract collection device to the topplate.

Note: If waste material (>1% of originalsample weight) has obviously adhered to thecontainer used to transfer the sample to theZHF determine the weight of this residueand subtract it from the sample weightdetermined in section 7.3.4 to determine theweight of the waste sample that will befiltered.

Attach a gas line to the gas inlet/outletvalve (bottom flange) and, with the liquidinlet/outlet valve (top flange) open, beginapplying gentle pressure of 1-10 psi (or moreif necessary) to force all headspace slowlyout of the ZHE device into a hood. At the firstappearance of liquid from the liquid inlet/outlet valve, quickly close the valve anddiscontinue pressure. If filtration of the wasteat 4 °C reduces the amount of expressedliquid over what would be expressed at roomtemperature, then allow the sample to warmup to room temperature in the device beforefiltering. If the waste is 100% solid (seesection 7.1.1), slowly increase the pressure toa maximum of 50 psi to force most of theheadspace out of the device and proceed tosection 7.3.12.

7.3.9 Attach the evacuated pre-weighedfiltrate collection container to the liquidinlet/outlet valve and open the valve. Beginapplying gentle pressure of 1-10 psi to forcethe liquid phase of the sample into the filtrate

collection container. If no additional liquidhas passed through the filter in any 2 minuteinterval, slowly increase the pressure in 10psi increments to a maximum of 50 psi. Aftereach incremental increase of 10 psi, if noadditional liquid has passed through the filterin any 2 minute interval, proceed to the next10 psi increment. When liquid flow hasceased such that continued pressure filtrationat 50 psi does not result in any additionalfiltrate within a 2 minute period, stop thefiltration. Close the liquid inlet/outlet valve,discontinue pressure to the piston, anddisconnect and weigh the filtrate collectioncontainer.

.Note: Instantaneous application of highpressure can degrade the glass fiber filter andmay cause premature plugging.

7.3.10 The material in the ZHE is definedas the solid phase of the waste and thefiltrate is defined as the liquid phase.

Note: Some wastes, such as oily wastesand some paint wastes, will obviouslycontain some material that appears to be aliquid. Even after applying pressure filtration,this material will not filter. f this is the case,the material within the filtration device isdefined as a solid and is carried through theTCLP extraction as a solid.

If the original waste contained <0.5% drysolids (see section 7.1.2), this filtrate isdefined as the TCLP extract and is analyzeddirectly. Proceed to section 7.3.15.

7.3.11 The liquid phase may now be eitheranalyzed immediately (See sections 7.3.13through 7.3.15) or stored at 4C under minimalheadspace conditions until time of analysis.

Determine the weight of extraction fluid #1to add to the ZHE as follows:

20x percent solids (section 7.1.1)X weight of waste filtered (section 7.3.4 or 7.3.8)Weight of extraction fluid

26992.R 92



7.3.12 The following sections detail howto add the appropriate amount of extractionfluid to the solid material within the ZHE andagitation of the ZHE vessel. Extraction fluid#1 is used in all cases (See section 5.7).

7.3.12.1 With the ZHE in the verticalposition, attach a line from the extractionfluid reservoir to the liquid inlet/outlet valve.The line used shall contain fresh extractionfluid and should be preflushed with fluid toeliminate any air pockets in the line. Releasegas pressure on the ZHE piston (from the gasinlet/outlet valve), open the liquid inlet/outlet valve, and begin transferring extractionfluid (by pumping or similar means) into theZHE. Continue pumping extraction fluid intothe ZHE until the appropriate amount of fluidhas been introduced into the device.

7.3.12.2 After the extraction fluid hasbeen added, immediately close the liquidinlet/outlet valve and disconnect theextraction fluid line. Check the ZHE to ensurethat all valves are in their closed positions.Manually rotate the device in an end-over-end fashion 2 or 3 times. Reposition the ZHEin the vertical position with the liquid inlet/outlet valve on top. Pressurize the ZHE to 5-10 psi (if necessary) and slowly open theliquid inlet/outlet valve to bleed out anyheadspace (into a hood) that may have beenintroduced due to the addition of extractionfluid. This bleeding shall be done quickly andshall be stopped at the first appearance ofliquid from the valve. Re-pressurize the ZHEwith 5-10 psi and check all ZHE fittings toensure that they are closed.

7.3.12.3 Place the ZHE in the rotaryagitation apparatus (if it is not already there)and rotate at 30 ± 2 rpm for 18 ±t 2 hours.Ambient temperature (i.e., temperature ofroom in which extraction occurs) shall bemaintained at 22 __E 3"C during agitation.

7.3.13 Following the 18 ± 2 hour agitationperiod, check the pressure behind the ZHEpiston by quickly opening and closing the gasinlet/outlet valve and noting the escape ofgas. If the pressure has not been maintained(i.e., no gas release observed), the device isleaking. Check the ZHE for leaking asspecified in section 4.2.1. and perform theextraction again with a new sample of waste.If the piessure within the device has beenmaintained, the material in the extractorvessel is once again separated into itscomponent liquid and solid phases. If thewaste contained-an initial liquid phase, theliquid may be filtered directly into the samefiltrate collection container (i.e.. TEDLAR*bag) holding the initial liquid phase of thewaste. A separate filtrate collection containermust be used if combining would createmultiple phases, or there is not enough

volume left within the filtrate collectioncontainer. Filter through the glass fiber filter,using the ZHE device as discussed in section7.3.9. All extract shall be filtered andcollected if the TEDLAR ® bag is used, if theextract Is multiphasic, or if the wastecontained an initial liquid phase (see sections4.6 and 7.3.1).

Note: An in-line glass fiber filter may beused to filter the material within the ZHE if itis suspected that the glass fiber filter hasbeen ruptured.

7.3.14 If the original waste contained noinitial liquid phase, the filtered liquidmaterial obtained from section 7.3.13 isdefined as the TCLP extract. If the wastecontained an initial liquid phase, the filteredliquid material obtained from section 7.3.13and the initial liquid phase (section 7.3.9) arecollectively defined as the TCLP extract.

7.3.15 Following collection of the TCLPextract, immediately prepare the extract foranalysis and store with minimal headspace at4C until analyzed. Analyze the TCLP extractaccording to the appropriate analyticalmethods. If the individual phases are to beanalyzed separately (i.e.. are not miscible).determine the volume of the individualphases (to 0.5%), conduct the appropriateanalyses, and combine the resultsmathematically by using a simple volume-weighted average:

Final Analtye _ (Vi)(CJ)+(V2 )C 2 )Concentration -

where:V, =The volume of the first phases [L).C, =The concentration of the analyte of

concern in the first phase (mg/L).V* =The volume of the second phase (L).C 2 =The concentration of the analyt of

concern in the second phase (mg/L).7.3.16 Compare the analyte

concentrations in the TCLP extract with thelevels identified in the appropriate ,regulations. Refer to section 8.0 for qualityassurance requirements.

8.0 Quality Assurance8.1 A minimum of one blank (using the

same extraction fluid as used for thesamples) must be analyzed for every 20extractions that have been conducted in anextraction vessel.

8.2 A matrix spike shall be performed foreach waste type (e.g.. wastewater trotmentsludge, contaminated soil, etc.) unless the

result exceeds the regulatory level and thedata is being used solely to demonstrate thatthe waste property exceeds the regulatorylevel. A minimum of one matrix spike mustbe analyzed for each analytical batch. Thebias determined from the matrix spikedetermination shall be used to correct themeasured values. (See sections 8.2.4 and8.2.5.) As a minimum, follow the matrix spikeaddition guidance provided in each analyticalmethod.

8.2.1 Matrix spikes are to be added afterfiltration of the TCLP extract and beforepreservation. Matrix spikes should not beadded prior to TCLP extraction of the sample.

8.2.2 In most cases, matrix spikes shouldbe added at a concentration equivalent to thecorresponding regulatory level. If the analyteconcentration is less than one half theregulatory level, the spike concentration maybe as low as one half of the analyteconcentration, but may not be not less thanfive times the method detection limit. In orderto avoid differences in matrix effects. Lhe.matrix spikes must be added to th- samenominal volume of TCLP extract as thatwhich was analyzed for the unspiked sample.

8.2.3 The purpose of the matrix spike is tomonitor the performance of the analyticalmethods used. and to determine whethermatrix interferences exist. Use of otherinternal calibration methods, modification ofthe analytical methods, or use of alternateanalytical methods may be needed toaccurately measure the analyte concentrationof the TCLP extract when the recovery of thematrix spike is below the expected analyticalmethod performance.

8.2.4 Matrix spike recoveries arecalculated by the following formula:%R (% Recovery)=100 (X$-X.)/K

where:X,=measured value for the spiked sample,X,=measured value for the unspiked sample,

andK= known value of the spike in the sample.

8.2.5 Measured values are corrected foranalytical bias using the following formula:X, = 100 (XJ%R)

where:X=corrected value, andX.=measured value of the unspiked sample.

8.3 All quality control measures describedin the appropriate analytical methods shallbe followed.

8.4 Samples must undergo TCLPextraction within the following time periods:

I I I I II •

2699,1


26994 Federal Register / Vol. 55, No. 1261 Friday, June 29,. 1990 Rules and- Regulations

SAMPLE MAXIMUM HOLDING TIMES (DAYS)

From.. FromFrom: TCLP prepa - t

tive TofFcollection ec extraction elapsedtU,.TCLP Prepara- determi-extration tive native

extraction av*snalysis__

Voaits........ . .... .......... . .......... .......................... ............. ........ 1'4 NA' 14 211Semvoltils ....... 1, T' 40' Q

Marcur .... . . 28. INN 29, 56i

Metal *exc*tmerc. ...... 180 NA 180. 360

NA=Ndt applicable.

If sample holding, times are exceeded,the values obtained will be consideredminimal concentration. Exceeding theholding time is not acceptable: inestablishing that a waste does not'exceed the regulatory revel. ExceedingthW -bld ng time will not-inalidatecharacterization. ifthe waste exceedsthe regulatory level.

TAtr t.-VOATtLE ANALYTES "

Compound! CAS No.

Acetone . .67-64-1

71-36-3Carbon.dud~. ........... 75.45-0oCarbon tetachr ............. 56-23-5Chlorobenzene.............................. 108-90-7

Chloroform.. ... 67-66-31,2-Dichloroethanff .. . 107-06-21,1-Dichloroeyle... ... 75-35-4Ethyl aceta-....... _ ........ 141-78-6Ethyl benzene............. .. .. 100--41-4Ethyl ether ............................ 60-29-7Isobutana, 78-83-4M an ............... 67-56-1Mathylene chlorde ................. 75-09-2IMethllethyl.lketone_ ..................., 70.93-3

Methyl isb .ketone..._- _.. 108-t0-1Tetrachloroethylene . 127-18-4Toluene,_ .... . . . ..... .. 1 8 -

1,1,1,.-Trichloroethane ................... 71-55,-8Trichioroethylene. ........................ 79-01-4TrichlorofluorQmethane.._................ 75-4941.1,2-Tdchloro-t1,2,2-trtfluoroethane _.. 76,-t3-1Vinyl chloride. ...................... 75;-01:-4

'When testI for any or- alt ot these. aelytes- thezero-headspace extractor vessel shall; be used In,stead of. the. bottle extractor.

" Benzene. carbon tetrachloride, chloroberzene,chloroform;, T.2-d hotmrehane, t,l-dichlooet-hylene,methyl ethyl ketone, tetrachloroethylene, trichlor-oethylene, and vinyl chloride are toxicity characteis-tic constituents.

TABLE 2.-SUITABLE ROTARY AGITATION

APPARATUS s

Company. [f ocation, Model No.

4-vesset(DC20S), 8-vessel,(DC20), 12-vessel(DC20B)

TABLE 2.- SUITABLE ROTARY AGITATION;APPARATUS -Continued

Company Location , Model No.

AssocateDesign endManutactur-ing Company..

EnvironmentalMachine and"Design, Inc.

IRA MachinerShop and'Laboratory.

Lars LandeManufactur-ing.

Milipore Corp.._

Alexandria. VA,(703) 549-5999-

Lynchburg, VA,(804)84.-6424.

Santurce, PR(809) 752-4004.

Whitmore Lake,MI, (313)449-4116&

Bedford M&(800225-3384;

2-vessel (3740 -2 4vessel;

(3740-4)., 6-vessel (3740-6) 8,-vessel(3740-8), 12-vessel (3740-12L 24 -vessel (3740-24.

8-vessel: (0-00-00).4-vessel (04-00-00)

a-vessel,(011001).

10-vessel(01VRE)5-vessel(5VRET.

4 -ZHE or41-ftef, bottleextractor,(YT00RAJ,".

IAny device that rotates. the extraction vessel, Inan end-over-end fashion at 30 + 2' rpm is accepta-ble .

TABLE 3-SUITABLE ZERO-HEADSPACEEXTRACTOR VESSELS'

Company, Location Model No,

Analyticar Warrlngl n, PA. C102;Testing & (215) 343- MtcharConsulting- 4490. PressureLSevices, Inc_. Device.

Associated Alexandria VA. 3745-ZHE, GaDesign and (703) 549- PressureMarufactur- 5999. Device.ing Company.

Lars Lands Whitmore Lake, ZHE-1 1. GasManutactur- MI. (313) Pressureing= 449-4116. Device.

Millipore r Bedford, MA, YT30090HW,Corporation. (800) 225- Gas Pressure

3384. Device.Environmental. Lynchburg, VA, VOLA-TOXI,

Machine and (804). 845- Gas PressureDesign Inc.. 6424. Device.

IAny device that meets the specifications listed insection 4.2.1'. of the method Is acceptable.

IThis device uses a 110 mm filter.

TABLE 4.-S UIrABLE FILTER HOLDERS 1

Company Locaslo Me, Sim

Nucdeo- Pleasan- 425910. 142mm;.pore. ton. 410400; 47Corpo- CA., mmration; (800)

882-7711'.

Micro Dubft 307400, t42- mm,Fitra- 'A.. 1 3 1i400, 4don (8001' mfnmsys- 334tems. 7132,

(415'828-6010.

Milipore Bedford, YT30142HW 142 mm,Corpo- MA, XX100 70' 47,ratoni (00 mm.

22-3384".

Any device capable: 0 separa; the. liruid, from,the solid phase o the waste is swtable, prowv"Jtha it is chemically comtpetible with the waste andthe constituents Io bes nyzad. Plastic devices (notlisted above)' maybe used whem only Inorganianalytes. are.of concern. The. 142 mm size filtWeholder is. recommendad

TABLE 5 .- SUITABLE FILTER MEDIA'

1Pore.Company Location, Mode Size

Miflipore. Bedford. A. . AP4O 0.7Coiporatiorn (800) 225-

3384.Nudeopore Pleasanton, 211625 '07

Corporation. CA, (415)463-2531Y.

Whatmar Clifton. NJ GFF' 0:7Laboratory 1 (201-773L-Products;. 580.Inc..

Micro Filtration Dublin, CA, GF75 0.7Systems. (800) 334-

7132, (415)828-6010.

Any filter that meets the specifications in section4.4 of the Method is suitable.

BILUNG CODE 6560-50-M

Analytical:Testing andConsulting.Services, Inc.

Wanington, PA.(2115Y 343-

II II


Federal Register / Vol. 55. No. 120 / Fridav Tuna 90 loon I P. .1 nt Ra"In;.,If II 0 I AD C

Rotary Agitation ApparatusFigure 1.


26996 Federal Register / Vol. 55, No. 126 / Friday, June 29, 1990/ Rules anct Regulations

Uquid Inlet/Outlet Valve

Top Flange -...

Support Scree ~

Filter .:. .

Support Scree - .. Samplea~~~pl~~~r """-,.. ... .. ... ...... •...... '. o... ""

:; .. .... .. : . ...... :) --....- .-. . . .

. . . . . . . .. _.;.,.. ............ ..... *.. ... ,,:

• ....... '. ,. ... -***.'.." - . -: .. -e.'; :•" ;:".'-

Bottom Flange-O

Pressurized Gas-.

Inlet/Outlet, Valve Presue

, ". ,".;j- ,.';•• ":" " .'' G auge'.-; ....D. .. :,'

Figure 2. Zero-Headspace Extractor (ZHE)


Federal Register / Vol. 55, No. 126 / Friday, June 29, 19g / Rules and Regulations

METHOD 1311

TOXICITY CHARACTERISTIC LEACHATE PROCEDURE

glass fiberfilter

What isthe 7

solids in thewaste?

Separateliquids fromsolids with

0.6 - 0.8 urmglass fiber

filter

Solid

Yes

Extract withappropriate fluid

1) Bottle extractorfor non-volatiles2) ZHE device for

volatiles

26997



METHOD 1311 (CONTINUED)

TOXICITY CHARACTERISTIC LEACHATE

Separateextract fromsolids with

0.6 - 0.8 urnglass fiber

filter

PROCEDURE

Combineextract withliquid phase

of waste

[FR Doc. 90-15048 Filed 6-28-90 8:45 am]BILLING CODE 656-50-C

Measure amount ofliquid and analyze

(mathematicallycombine result with

result of extractanalysis)

-26998


this information is reproduced with permission from ... register / vol 55, no. 126 friday, june 29,...

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